Complex copper compounds of disazo dyestuffs



Patented Jan. 16, 1951 UNITED ESTATES PATENT OFFICE 2,538,568 'COMPLEXOF DIS'Z DYEsTUFFs om Kaiser; normen, willy Widmer., Bptimine een,ArthurBuehlri` Rheinfelden, .and Chris- No Drawing. Appiieetim June-Vv,1948,., serial -In 'Switzerland July 4, 1947 l wording to this inventionValuable new azoiye"stuii`.sv are lobtained:by coupling a' diazo-coin'-pound of an amino of the general -fo'rmula e. OH

ent invention, 'inereinas'f 'be' mentieaespee 1 those of which theradical R is a hydrocarbon radica-l containing up to 7 carbon atoms asfor inta-nce 3arnino-4hydroxyl-acetophenone, (3-agmino-i-hydroxy-phenyl) -n-propyl ketone, (3- a'rnino-i-hydroXy-phenyl)-n-butyl ketone, (3- ,anno-i-hydroxy-phenyl) -n-amyl ketone and 3-amino-i-hydroXy-Z' -carboxyediphenyl ketone.

The coupling components serving as starting materials in the presentinvention may owe their capacity for coupling, for example, to an aroenegroup, Depending' en the choice of the cou-V` pling components there canbe obtained in this manner, fe exenime, metanzable meneame-'dyes stuffsare sparingly Soluble to insoluble in winter and 'semble een' 'ese esterie'cquers, er watere'sol-uble morioazo-dyestuffs, which advanta'gee'u's'ly 'contain suliolnic acid groups, 'and which areprinci'pallgy` suitable' for dyeing an'majl'iibers, but 'alsof'aZ-dyestui's which are suitable for dy# ingceuulosic materials', forexample, those dyestuf'f's wh'ie'ncentain a' 'pluality'e eze-groups,feui-` vatagieously disazoi-dyestulti's.

dei teieiodiiee by ine 'present ini/eenen meneeeee'dyeetufis which aiespannen-semble te E invention those coupling components which arecapable .of imparting substantivity for c-ellulosic bers to the dyestufsor of enhancing their substantivity for Vcellulosic bers. For thispurpose there come into consideration above all N-substitutedderivatives of 2-amino-5-hydroxynaphtha- ,lene-'l-suifonic acid andespecially those N-substituted derivatives or 2-amino5-hydroxynaphthalene--sulfonic acid which are capable of coupling twice such, forexample, as the compounds containing two radicals ofehydroxy-naphthaaminoazo-dyestui simultaneously or in succession with 1molecular proportion of the heterocyclic bridge member, and, when a freehalogen atom is still present (for'example,l iii-condensing withcyanuric chloride), a further reaction, for example, with aminobenzene,may be carried out. In this manner either symmetrical or asymmetri- .caldyestufs may be made.

lene--sulfonic acid which radicals are linked together in theirZ-positions by means of a bridge member and each of which is bound inits 2-position to a nitrogen atom. These bridge members preferably maybe built up in such manner that the direct chain which links the tworadicals ofA 5-hydroxy-7-sulfonic acid together contains from one to veatoms. The compounds of this type which contain symmetrical bridgemembers are especially valuable. As examples then can Vbe mentioned inthis connection:

Above all 5:5 -dihydroxy-Z :2 -dinaphthylurea- 7:7disulfonic acid, butalso 5:5dihydroxy 2:2dinaphthylamino'? :7-disulfonic acid, and alsocondensation products in which two molecules ofZ-amino--hydroxynaphthalene-'l-sulproportion or 2:4-dichloroquinazolineand 2 mo` lecular proportion of 2amino5hydroxynaph thalene-'Y-sulionicacid. With such derivatives of 2 amino 5 hydroxynaphthalene-'-sulfonicacid capable of coupling twice and the diazocomponents of amines of theabove general formula there can be made, for example, symmetricaldisaZo-dyestuis. Especially good properties are exhibited by theasymmetrical disazo-dyestuffs which are obtained by coupling 1molecularl proportion of a derivativeo-f2-amino-5-hydroxynaphthalene-'-sulonic acid capable of coupling twicewith 1 molecular' proportion of a diazocompoundof amine of the aboveformula and 1 molecular proportion of another diam-compound,advantageously one which contains in a position vicinal to thediazo-group a group which is capable of taking part in the formation ofmetal complexes, for example, a diazo-compound of the benzene seriescontaining such a group as for instance a hydroxyl group. For thispurpose there come into consideration, for example, the dia'zo-compoundsof the following amines: 2-A amino l hydroxybenzene 4 sulfonic acid, 6-chloro-Z-amino 1 hydroxybenzene 6 sulfonic acid, 2amino1hydroxyben2ene 4carboxylic acid anilide, 2-amino-lhydroxybenZene-4-carb oxylic acid nbutylamide, 1 aminobenzene-Z- carboxylic acids and their nuclearsubstitution products, and 2-amino-l-methoxybenzene-l-sulionic acid.

n The dyestuffs obtainable from the condensation products of 2 molecularvproportion of 2-amino- 5hydroxynaphthalene7-sulfonic acid andl-molecular proportion of a heterocyclic bridge member in themanner-described above may also be made by rst coupling thediazo-compound with 2 amino-5-hydroxynaphthalene-7-sulfonic acid andthen linking 2 molecular proportions of the As examples of compound ofthe fri The' diazotizationv of the amines of the above general formulaused as starting materials in the present invention may. be broughtabout by the usual 'known methods, for example, with the aid 1of sodiumnitrite in a medium rendered acid with hydrochloric acid.- vThe couplingis generally carried out with'advantage in an alkaline mediumforexample, a medium rendered alkaline with-alkali carbonate or alkalihydroxide.

In couplingwith derivatives of 2-amino-5-hydroxy-4nap'hthatler'ie-JI-sulfonic acid capable of coupling twice itisgenerally of advantage to work in a medium containing calcium hydroxide.If desired, the coupling may also be'conducted inthevl presence of a`suitable solvent 'suchas alcohol or pyridine.

The azo-dyestuis obtainable by the present invention are new andcorrespond to the general formula in which Rv representsjan valkyl oraryl residue, andR1 represents the radical originating'from' `a couplingcomponent which containsa hydroxyll ing-a very wide "variety ofrmaterials.

The dyestuis may be treated with agents yielding nietaLand'tllistreatm'a mannerin itself' knojwni Thus, for example, the m eral `formula inwhich R represents an alkylor aryl residue,-

and R1 represents the residue of ac'oupling-com'-, ponent which containsa hydroxyl group in av position vicinal-to the -N=N-linkage, are con-Jverted into complex metal compoundsv by treat-Al ment in substance withagents yieldingmetal. As lagents yielding metal there come into com.sideration in this connection, forexample, agents yielding iron, nickel,cobalt, aluminium,. man-z ganese, copper,v and above all chromium.. Theltreatment with an agentyieldingmetal is` adf. vantageously carriedoutjbythe ,process rof Uf; S., patent application Ser. No. 774,879, filedSeptem-Y ber `18, 1947,- in ai neutral -to alkaline medium in thepresence of an aromatic o rtho-hydroxy:y carboxylic acid or salt thereofin such manner l Y azofdf'esaiffs, free, from suifo'm" acidgroupsiandrihavmg margen;

:assesses aniple v1. The diazo'solution is added toa solution Vof 22.4parts of 1-hydroxynaphthalene-4- sulfonic acid, 5.6 parts of potassiumhydroxide and 13.81parts of potassium carbonate in 160 parts ffwater at5 C.l .The whole is stirred for ia further 4 hours, while thetemperature. is allowed to rise slowly to 20 C. When the coupling hasceased the resulting dyestuff of the formula Eample 3 "It" 32.8 parts ofthe sodium saltjof the dyestuii from diazotized3amino-4-hydroxyacetophenone and 2-hydroxy-naphthalene and correspondingtothe formula .Ha 4 1; r1., I: are suspendedin 200 parts of water. 204parts of a solution of potassium-sodium chromosalicylate having '"achromium content of 1.53 per cent. are added. The solution ofpotassium-sodium chromosalicylate is obtained, for example, by boiling43.4 parts of a chromic sulfate solution having a chromium content oi7.2 per cent with 16.6 parts of salicylic acid and 100 parts of water,

dissolving the resulting precipitate by the addiv ti'onof 22 parts ofsodium hydroxide solution of 33 per cent. strength and 22 parts ofpotassium "hyd'roxide solution of 37 per cent. strength. After bo'ilingthe whole for 6 hours the chroming ceases. .'Acetic acid is' added untilthe reaction is acid to j litinus, l the dyestuff is separated byfiltration, 'wshedand drie-d. The chromed dyestuff lis a Violet powderwhich is sparingly soluble in water -and dissolves in alcohol with awine red coloration. By means of a solution ofthe dyestui in a'nitrocellulose lacquer there are obtained reddish-violetv coatings onsuitable substrata.

Eample 4 35.8 `parts o f the 'sodium salt of the dyestuff fromd'azotized' 3amino-4-hydroxyacetophenone and l phenyl 3 methyl- 5Dyrazolone are chromed in the manner described in Example 3.

Thev dried dyestuff is an orange-brown-powder which is sparingly solublein water` and dissolves easily in alcohol .with an orange coloration. Bymeans of4 a solution of the dyestuiin a nitro;4 cellulose lacquer orangecoatings are obtainedl'on suitable substrata.

The v diazo solution obtained from 15.1 parts of3ainino-4-hydroxy-acetophenone as described in Example 1 is added at.5-8'C. to a solution'of 22.4 parts of -2fhydroxynaphthalene-6-sulfonicacid, 4.2 parts" of sodium hydroxideV and 1 2 parts. of sodium carbonatein parts of wat`,"and' stirred at the same temperature until theformation of dyestui ceases. The' resulting dyestuil' ofthe formula .H3is separated by ltering with suction, and ifde sired purified bydissolution in water and '1`ep 'rc cipitaton .with sodium chloride,andfdried. vIt a grey powder whichA dissolves in water witha violetcoloration, in,.' c'oncentrated sulfuricl acid with a. yellowish redcoloration, and dyes` wqo `l from an Yacid bath brown-'red `tints,.which when after-:chromed becomefviolet tints'of good f tness tofulling and lightf" i Example 6 41.6 parts ofthe dyestuff'obta'ined asdescribed in ther's't paragraphof 'Example I are-boilediii a reflux'apparatus for a longtime in 150'0 parts of chromium fluoride solutioncontaining 6 .6 parts of chromium. The complex chromium compound isprecipitated from the solution, by the yaddition of sodium chloride. byfiltration and dried. The dyestuff isa brownredpowder which) dissolvesin water 'with anbrange coloration and infcon'- centrated 'sulfuric acid'with' a vgreenishyellc'w coloration, and dyes wool"f rom' a ""dhamm-ange tints .havingacqd proper f ness. [Complex chromiumcompoundshaving properties are obtained by startingfrom th'e d ejstufsdescribed in the'jsecond paragraph oIjjExgample l, andcarr'ying out'thechroming'o'peration in the manner'describedabove. f- .:Ezcamplei7 i.1,-. :i: .e

42 parts of thedyestuii obtainable as described Iin the rst paragraplfiof Example 2 are boiled in a reux apparatus for24hours in 120 parts ofchromium sulfate solution-containing 6.6 parts 'of chromium,'Theresulting conjiplex 'cciripoundf is; Worked up in. the! 'lisulimnaand in the dry'st'a'teitisy a greyfpowder which dissolves in water withai bluishlredf'cglora ion 'and' in concentrated sulfuric acid Witliolorationjand dyes wool from a sulfuricj" mmpz'ef 15.1 parts of3-amino-4-hydroxy-acetophenone arev diazotized in .themanner described.in Example l, andthe diazo compound is coupled. with 36.8'parts of theternary condensation product `from `1 molecular proportion of cyanuricchloride, 2 molecular proportions of2-amino-5-hydroxynaphthalene-'I-sulfonic acid and 1Y molecularproportion of aminobenzene, which product is dissolved in theforrn o itssodium salt in 500 parts of water with the addition of 50 parts of asuspension of calcium hydroxide of 20 per cent. strength. After 4 hoursthe dyestui so obtained is precipitated by means of hydrochloric acidand separated by ltration. The i'llter residueis dissolved lin the formof its sodium salt. The dyestuff of the formula EN H Ho 0H Ho N=N N/ N-N= Boas' NE1L, Ji-HN scant co N cito H3 on;

Tlie'm'ixed' diazotization product obtained in the usual manner from22.8 parts of 2-amino-1-hydroxybenzene-4-carbxylic acid phenyl amide/and15.1 parts of 3-amino-4-hydroXy-acetophenone is coupled with 50.4 partsof the urea of 2-amino- -hydroxynaphthalene-7-sulfonic acid, which isdissolved. in 1000 parts of water in the form of vits sodium -salt"withthe addition of '100 parts *of'a'sus'pension of calcium 'hydroxide of2010ercentstrength. After 4 hours the resulting dye- *stuit isprecipitated bythe addition of hydrochloric acid, and separated byfiltration. The lter residue is converted into its complex copper`compound in known manner by the addition of a solution of 50 parts ofcrystalline copper sulfate in 200l parts of ammonia solution of 25 percentstrengthand 200 parts vofwater at TIO-75 C. The copper compound soformed ofthe dyestuff i. of the formula on ff'1 ".'fia 1" precipitated.by the addition of 5'0 lparts of sodium chloride, separated byltratiouand dried.

flhenew cupriferous dyestuff is a dark powder which dyes cotton bordeauxtints. The dyeing is fastl tcwashingand light.

`By using, instead of 2-amino-l-hydroxybenzene-4-'carboxylic acid phenylamide, 2-amino-lhydroxybenzene-4-sulfonic acid or the sulfonamide thereo1; 6-chloro-2-amino-l-liydroxybenzene- 4 ieulfbn ci'acd there areobtained dyestufs naving similar properties. By replacing in the aboveexample the urea of 2-amino--hydroxynaphthalene-'Z-sulfonic acid by theternary condensation product from 1 molecular proportion of cyanuricchloride, 2 molecular proportion of 2-amino-5-hydroxynaphthalene-7-sulionic acid and 1 molecular pro-portion ofaminobenzene there is obtained a dyestuff having similar properties. .vA bluish-violet dyestuil is obtained by using 5 :5 -dihydroxy-2 2-dinaphthylamine-7 :7 -disulfonic acid, instead of the above mentionedurea of 2-amino-hydroxy-naphthalene- 7 sulfonic acid.

` Example 1.0

The mixed diazotization product which is ob- .tained in the usual mannerfrom 18.8 parts of Z-amino-l-hydroxy benzene-4-sulfonic acid :amide and17.9 parts of (3-amino-4-hydroxy on no no f' Q .rmn 'A no .NH-c-HN scany v o ma phenyl) -n-propyl ketone are coupled With `50.4 parts of theurea of 2amino--hydroxynaphthavlene-'T-sulfonic acid, which is dissolvedin the Vform of its sodium salt in 1000 parts of Water with the additionof 100 parts of a suspension of calcium hydroxide of 20 per cent.strength. After 4'hours the dyestui formed is precipitated by theaddition of hydrochloric acid and separated byi'lltration. The lterresidue is converted into its complex compound in known manner bytreatment with a solution of 50 parts of crystalline copper sulfate in200 parts of ammonia solution of 25 per cent. strength and 200 parts ofwater at 'T0-*75 C. The copper compound so formed of the dyestuff of theformula vSO2 co mii-crm Example `11 The mixed diazotization productwhich is ob- Y tained in the usualmannerhfrom 22.3 parts of 6-fchloro-2-arnino 1 hydroxybenzene 4 sulfonic 'aci'dand 15.1 parts of4-hydroxy-3-amino acetophenone are coupled with 60.4'parts of theconfdensation product from 1 molecular proportionaof 2chloro-.quinazolinefand 2 molecular propor-2farnino-'15-hydroxynaphthaieneJl :Sul-

g Il acid. which. is dissolved in the iormlof 11 i, vits sodium salt in2000 parts of Awater with the addition oi 100 parts of a suspension lofcalcium hydroxide of 2'0 per cent. strength. After 4 hours thedyestuii"` formed is precipitated by the addition of, hydrochloric acidand separated by filtration. The filter residue is dissolved in the formof its sodium salt. The c yestuc of the formula is precipitatedfr'ornthesolution by means vof proximately neutral reaction are added,coppering is carried on at about 80 C., for 1/2 hour, and the goods arethoroughly rinsed with cold wai YHo ter. A ruby reddyeing is obtainedwhich is of sodium chloride, separated by ltration and dried. "52,0 goodfastness to washing and light.

It is a black powder which dyes cotton from .a weakly alkaline bath redtints. By the addition to the dyebath of a copper salt solution preparedfrom copper sulfate and sodium tartrate .the tint .v is changed towardsred-violet.

fast to-washing and light.

The dyeing is By using in the aboveV example, instead of 6- acidphenylamide a dyestui having similar properties is obtained.

-. Y The dyestuis described inxamples .9i tof12 hereinbefore can also beobtained-by coupling first one of the two diazo compounds withthe.

coupling component and then coupling with the monoaZo-dyestui`-soobtained the other diazo compound. The dyestuffs obtained in vthis wayhave practically the .same properties as those ob'- tained in accordancewith the prescriptions given above.

Example 12 p 100 parts of well wetted wool are entered at 60 C. into adyebath which contains in 4000 parts of water 1 part of the dyestuffobtainableas d- '1- scribed in Example 5, 4 partsoffacetic'acid of 40per cent strength and `parts of crystalline sodium sulfate.` Thetemperature is raised to the boil in the course of minutes and dyeing iscarried o-n at the boil for minutes.

is then cooled to about '70 C., 1 part of potassium bichromate is added,and the whole is brought to the boil and chroming is carried on for 40minutes l at the boil. Thevwool is dyed a fast violet Ercample 3 1000parts of well wetted woollare entered at C. into a'dyebath whichcontains in -3000 parts of water 1` part ofthe dyestuff obtainable asdescribed in Example?, and 40;' parts' of sulfuriof..V

100 parts of cotton are entered into Aa dyebath at 50 C. containing in4000 parts of water 2 parts vof anhydrous .sodium carbonate .an d1.0.7part of the dyestui obtainable'.as-described inthe rst paragraphoijExample- 8;" 1The tempera- ?ture of the bath. is slowly raisedztothe.b0il;:3.0

The dyebath ""'O Ewample 15 A dyebath is prepared from 3000 parts ofwater, 2 parts of anhydrous sodium carbonate, "-1

r 275 part of the dyestu'ifV obtained as described in the firstparagraph of Example 9, and 30 parts of crystalline sodium sulfate. 100parts of cotton are entered into the dyebath at 40 C., the `ternperatureis raised to C., and dyeingmis 30 carried on at this temperature for 1h0ur. 'The cottonis then rinsed andA dried. j It is dyeda. bordeauxtint, and the dyeing is distinguished by -good fastness to washing andlight. What weY claim is:

1. A complex copper compound of a disazo dyestu of the general formula4infwhich-R and R4 each stands for a hydrocarbon-radical containing up to'7 carbon atis.

www

13 14 y 4. A ooml'lex oo'pper compound of the disaz REFERENCES CITEDdyestu ofthe formula Th following vreferenc'es are of rcord in the (imHO 0H H0 le of this patent:

N='N o Nt" s y UNITED STATES PATENTS H033 NH HN` 50m Number ,v Name Dat1,338,414 Anderwert et a1. Apr. 27, 1920. lo I 0 1,994,116 Straub et a1Mar. 12, 1935 am n-043, 2,217,693 M cNany et a1 oct. 15, 1940- 5. Acomplex copper compound of th'e disazo lo 2317'365 Dickey et al Apr' 27194-3\ dyestu of the formula 2,390,152 Keller Dec. 4, 1945 2,393,652Olpin et a1. Jan. 29, 1946 0E H0 0H H?, 2,438,754 Krebser et a1 Mar. 3o,194s j N (d 16 no. NH-o-HN -som o so, odi NH, "20

oTTo KAISER. Y

WILLY ARTHUR BUEHLER. v CHRISTIAN ZICKENDRAHT.

1. A COMPLEX COPPER COMPOUND OF A DISAZO DYESTUFF OF THE GENERAL FORMULA